JP2006259438A - Radiation-sensitive resin composition, protrusion and spacer formed of the same, and liquid crystal display element equipped with them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which is suitably used for simultaneously forming protrusions and spacers of a vertical alignment liquid crystal display element. <P>SOLUTION: The radiation-sensitive resin composition for simultaneously forming the protrusions and the spacers for the vertical alignment liquid crystal display element contains: a copolymer [A] of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (a1), an epoxy group containing unsaturated compound (a2), an unsaturated compound (a3) containing at least a group selected from a group of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a lactone skeleton, an oxyethylene skeleton with two to ten repeating units, and an oxypropylene skeleton with two to ten repeating units, and an olefinically unsaturated compound (a4) other than (a1), (a2) and (a3); and a 1,2-quinone diazide compound [B]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive resin composition for forming protrusions and / or spacers for vertical alignment type liquid crystal display elements, protrusions and spacers for vertical alignment type liquid crystal display elements formed therefrom, the protrusions and / or The present invention relates to a vertical alignment type liquid crystal display device provided with the spacer, and a method for forming the protrusion and / or the spacer.

  Liquid crystal display elements are most widely used in flat panel displays. With the recent spread of OA equipment such as personal computers and word processors and liquid crystal televisions, TFT (thin film transistor) type liquid crystal displays (TFT-LCD) The required performance for display quality is becoming stricter. The most widely used method among TFT-LCDs is a TN (Twisted Nematic) type LCD, which is a substrate having two transparent electrodes (hereinafter referred to as “transparent electrode substrate”). A polarizing film having a different orientation direction by 90 degrees is disposed on the outside, an alignment film is disposed on the inner side of the two transparent electrode substrates, and a nematic liquid crystal is disposed between the two alignment films. This is twisted 90 degrees from one electrode side to the other electrode side. When non-polarized light is incident in this state, the linearly polarized light transmitted through one polarizing plate is transmitted through the liquid crystal while the polarization direction is shifted, so that it can be transmitted through the other polarizing plate, resulting in a bright state. Next, when a voltage is applied to both the electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal is transmitted as it is, so that it cannot be transmitted through the other polarizing plate, resulting in a dark state. Thereafter, when the voltage is not applied again, the light state is restored.

Such a TN-type LCD has the same or better contrast and color reproducibility in the front than the cathode ray tube (CRT) due to recent technological improvements. However, the TN type LCD has a big problem that the viewing angle is narrow. As a solution to such a problem, an MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment type liquid crystal display) has been developed. As described in Non-Patent Document 1 and Patent Document 1, this MVA-type LCD has a negative-type liquid crystal having negative dielectric anisotropy and a vertical alignment film instead of the optical rotation mode of TN-type LCD. Combined birefringence mode is used, and even when no voltage is applied, the alignment direction of the liquid crystal located near the alignment film is maintained almost vertical, so it has excellent contrast, viewing angle, etc. It is also excellent in terms of the manufacturing process, such as not having to perform a rubbing treatment for aligning the liquid crystal.

In the MVA type LCD, as a domain regulating means for allowing the liquid crystal to take a plurality of orientation directions in one pixel region, a display-side electrode has a slit in one pixel region, and light A projection (for example, a triangular pyramid shape, a semi-convex lens shape, etc.) having a slope at a position different from the slit of the electrode is formed in the same pixel region on the incident side electrode substrate. In general, in a conventional liquid crystal display, a spherical or rod-shaped spacer such as a resin or ceramic is used in order to maintain a constant gap (cell gap) between two transparent electrode substrates. When the two transparent electrode substrates are bonded to each other, the spacer is dispersed on one of the substrates, and the cell gap is determined by the spacer diameter.
Further, in order to avoid the occurrence of problems such as cell gap non-uniformity due to variation in spacer diameter, Patent Document 2 proposes a method of forming protrusions and spacers using a photoresist. Has the advantage that fine processing is possible and the shape can be easily controlled. However, Patent Document 2 does not specifically describe the composition of the photoresist, and the performance of the formed protrusions and spacers is not clear.

Arihiro Takeda, Liquid Crystal, Japanese Liquid Crystal Society, April 25, 1999, Vol. 3, No. 2, 117 Japanese Patent Laid-Open No. 11-258605 JP 2001-201750 A

Examples of the performance required for the photoresist used for forming the protrusions and spacers for the vertical alignment type liquid crystal display element include the following items. In other words, the protrusions and spacers have appropriate cross-sectional shapes, resistance to solvents used in the subsequent alignment film forming process, resistance to heat applied in the alignment film forming process, transparency, resolution, and remaining. High performance is required for film ratio and the like. In addition, the obtained vertical alignment type liquid crystal display element is required to be excellent in orientation, voltage holding ratio, and the like. The present applicant has already [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound, and (a3) a copolymer of other unsaturated compounds. , [B] an unsaturated polymerizable compound, and [C] a radiation-sensitive polymerization initiator, a radiation-sensitive resin composition for simultaneously forming protrusions and spacers, protrusions and spacers formed therefrom, and the protrusions and A liquid crystal display element having a spacer has been proposed (see Patent Document 3). However, the development of radiation-sensitive resin compositions useful for the formation of protrusions and spacers in vertical alignment liquid crystal display elements has just begun, and in response to the rapid spread of TFT-LCD and increasingly demanding performance requirements. Development of a new radiation-sensitive resin composition capable of forming protrusions and spacers having excellent performance has become an important technical issue.

JP 2003-29405 A

The present invention has been made in view of the above circumstances, and its problem is that a radiation-sensitive resin composition for forming protrusions and / or spacers for a vertical alignment type liquid crystal display element, more specifically, photo Vertical alignment liquid crystal display with excellent resolution and residual film ratio as resist, and can form protrusions and spacers with excellent pattern shape, heat resistance, solvent resistance, transparency, etc., and excellent alignment, voltage holding ratio, etc. An object of the present invention is to provide a radiation-sensitive resin composition capable of providing an element, and a method of forming protrusions and / or spacers for a vertical alignment type liquid crystal display element using the radiation-sensitive resin composition.

According to the present invention, the above objects and advantages of the present invention are firstly
[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “compound (a1)”),
(A2) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a2)”),
(A3) At least one group selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, a lactone skeleton, an oxyethylene skeleton having 2 to 10 repeating units, and an oxypropylene skeleton having 2 to 10 repeating units And an olefinically unsaturated compound other than (a4), (a1), (a2) and (a3) (hereinafter referred to as “compound ( a4) ”(hereinafter referred to as“ copolymer [A] ”), and [B] a 1,2-quinonediazide compound. This is achieved by a radiation sensitive resin composition for simultaneously forming protrusions and spacers of a vertical alignment type liquid crystal display element.

Secondly, the objects and advantages of the present invention are:
This is achieved by a protrusion for a vertical alignment type liquid crystal display element formed from the radiation sensitive resin composition.

Third, the objects and advantages of the present invention are:
This is achieved by a spacer for a vertical alignment type liquid crystal display element formed from the radiation sensitive resin composition.

The objects and advantages of the present invention are fourth.
This is achieved by a vertical alignment type liquid crystal display device including the protrusion and / or the spacer.

The purpose and advantage of the present invention are fifthly.
This is achieved by a method for forming protrusions and / or spacers characterized by including at least the following steps.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate.
(2) A step of irradiating at least a part of the coating film with radiation.
(3) Development process.
(4) Heating process.

Below, the detail of each component of the radiation sensitive resin composition in this invention is demonstrated.
Copolymer [A]
Copolymer [A] can be produced by radical polymerization of compounds (a1), (a2), (a3) and (a4) in a solvent in the presence of a polymerization initiator. In the copolymer [A] used in the present invention, the structural unit derived from the compound (a1) is added to the total of repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. When a copolymer having a constitutional unit of less than 5% by weight is used, it is difficult to dissolve in an alkaline aqueous solution during the development process, while a copolymer exceeding 40% by weight tends to be too soluble in an alkaline aqueous solution. .

Examples of the compound (a1) include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, poly [carboxylic acid] mono [(meth) acryloyloxyalkyl] esters, and polymers having a carboxyl group and a hydroxyl group at both ends. And mono (meth) acrylates, polycyclic compounds having a carboxyl group, and anhydrides thereof.
Specific examples thereof include, for example, acrylic acid, methacrylic acid, crotonic acid and the like as monocarboxylic acids;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
As anhydrides of dicarboxylic acids, anhydrides of the compounds exemplified as the above dicarboxylic acids, etc .;
Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc .;
As a mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, ω-carboxypolycaprolactone mono (meth) acrylate and the like;
Polycyclic compounds having a carboxyl group and anhydrides thereof such as 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl Bicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept -2-ene anhydride and the like can be mentioned.
Of these, monocarboxylic acids and anhydrides of dicarboxylic acids are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability. . These may be used alone or in combination.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a2) is added to the total number of repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the resulting protrusions and / or spacers tend to decrease, whereas when the amount of this structural unit exceeds 70% by weight, the radiation-sensitive resin composition The storage stability of the product tends to decrease.

  Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate. , Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. It is preferably used from the viewpoint of increasing the copolymerization reactivity, the heat resistance of the resulting protrusions and / or spacers, and the surface hardness. These may be used alone or in combination.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a3) is added to the total number of repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, it is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight. When this structural unit is less than 5% by weight, the developability of the exposed portions of the protrusions and / or spacers tends to be lowered. On the other hand, when it exceeds 50% by weight, in the development step in forming the protrusions and / or spacers, There exists a tendency for the solubility with respect to aqueous alkali solution to become large too much.

As the compound (a3), for example,
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl-de Hydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2-oxo- 3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl ester, 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester and the like;
Examples of the oxyethylene skeleton having 2 to 10 repeating units include polyethylene glycol (n = 2 to 10) mono (meth) acrylate and the like;
Examples of the oxypropylene skeleton having 2 to 10 repeating units include polypropylene glycol (n = 2 to 10) mono (meth) acrylate.

In the copolymer [A] used in the present invention, the structural unit derived from the compound (a4) is added to the total repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably less than 70% by weight, particularly preferably less than 50% by weight. If it exceeds 70% by weight, it may be difficult to dissolve in an alkaline aqueous solution in the development step in the formation of protrusions and / or spacers.
Examples of the compound (a4) include methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid esters having a hydroxyl group, acrylic acid cyclic alkyl esters, and methacrylic acid aryl esters. Acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, and other unsaturated compounds.

Specific examples thereof include, for example, methyl methacrylate, methyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, trimethyl methacrylate, and alkyl methacrylates. Decyl methacrylate, n-stearyl methacrylate, etc .;
Methacrylic acid cyclic alkyl esters such as methyl acrylate and isopropyl acrylate;
Cycloalkyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane as cyclic alkyl esters of methacrylic acid -8-yloxyethyl methacrylate, isobornyl methacrylate, etc .;
Hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside as methacrylic acid esters having a hydroxyl group 4-hydroxyphenyl methacrylate, etc .;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane as acrylic acid cyclic alkyl esters -8-yloxyethyl acrylate, isobornyl acrylate and the like;
Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
As unsaturated dicarboxylic acid diesters, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- as bicyclo unsaturated compounds 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] ] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyl Oxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2 .1] hept-2-ene, 5,6-di (cyclohexylo Xylcarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like;

As maleimide compounds, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide and the like;
As unsaturated aromatic compounds, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like as conjugated dienes;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, bicyclounsaturated compounds, unsaturated aromatic compounds, and conjugated dienes are preferably used, and styrene, t-butyl methacrylate, tricyclo [5. 2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene From the viewpoint of solubility and solubility in an aqueous alkali solution. These may be used alone or in combination.

Preferred examples of the copolymer [A] used in the present invention include, for example, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / tetrahydro. Furfuryl methacrylate copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / p-vinylbenzyl glycidyl ether / tetrahydrofurfuryl methacrylate copolymer, methacryl Acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / polyethylene glycol monomethacrylate copolymer, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / methacrylic Such as glycidyl / polypropylene glycol monomethacrylate copolymers.

The copolymer [A] used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 × 10 ^{3 to} 5 × 10. ⁴ is desirable. If the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, and the remaining film ratio of the resulting film may decrease, or the resulting protrusion and / or spacer pattern shape, heat resistance, etc. On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be inferior. The radiation-sensitive resin composition containing the copolymer [A] can easily form a predetermined pattern shape without causing a development residue during development.

Examples of the solvent used for the production of the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol alkyl ether acetates. , Propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like.
Specific examples thereof include, for example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol as alcohols;
Tetrahydrofuran as ethers;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
As diethylene glycols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
As propylene glycol monoalkyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether propionates, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;
As propylene glycol alkyl ether acetates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

Esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyacetic acid Ethyl, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy- Methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, propoxyacetic acid Chill, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropio Acid butyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid Examples thereof include esters such as propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol alkyl ether acetates are preferred. Particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate. Is preferred.

As the polymerization initiator used for the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2 Azo compounds such as' -azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypi Organic peroxides such as valates, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.
In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen Xanthogens such as sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[B] Component The [B] component used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”). And a condensate of 1,2-naphthoquinonediazide sulfonic acid halide can be used.
Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Specific examples thereof include, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like as trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
As pentahydroxybenzophenone, 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
As hexahydroxybenzophenone, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone, etc .;

As (polyhydroxyphenyl) alkane, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4- Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5 , 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like;

As other mother nucleus, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy-2) -Methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1 -(3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl)- 1-methylethyl} -1,3-dihydroxybenzene.
Further, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide Etc. are also preferably used.

Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol is preferred.
The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide. -5-sulfonic acid chloride can be mentioned, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

The use amount of the mother nucleus and 1,2-naphthoquinone diazide sulfonic acid halide used for the condensation reaction is preferably 1.0 to 4.0 mol of 1,2-naphthoquinone diazide sulfonic acid halide with respect to 1 mol of the mother nucleus. More preferably, it is 1.5-3.0 mol.
The condensation reaction can be carried out by a known method.
These [B] components can be used alone or in combination of two or more.

  [B] The usage-amount of a component becomes like this. Preferably it is 5-100 weight part with respect to 100 weight part of copolymers [A], More preferably, it is 10-50 weight part. When this ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution that is the developer is small, and patterning may be difficult. Alternatively, the heat resistance and solvent resistance of the spacer may be insufficient. On the other hand, when this ratio exceeds 100 parts by weight, the solubility in the alkaline aqueous solution may be insufficient in the radiation irradiated portion, and development may be difficult.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymer [A] and [B] components as essential components, but [C] a thermosensitive acid-generating compound, [ D] a polymerizable compound having at least one ethylenically unsaturated double bond, [E] an epoxy resin other than the copolymer [A], [F] an adhesion assistant, [G] a surfactant, or [H A cross-linking agent can be included.
[C] The heat-sensitive acid generating compound can be used to improve heat resistance and hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts.
Specific examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.
Specific examples thereof include, for example, 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimony as alkylsulfonium salts. Dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexanium as benzylsulfonium salts Fluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, etc .;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate as dibenzylsulfonium salts Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxy Phenylsulfonium hexafluorophosphate, etc .;
P-Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro as substituted benzylsulfonium salts Phosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4 -Hydroxyphenylmethylsulfonium hexafluoroantimonate etc. can be mentioned, respectively.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- Benzylbenzothiazonium such as methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Salt.
Of these, sulfonium salts and benzothiazonium salts are preferably used, particularly 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexanium. Fluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazolium hexafluoroantimonate are preferably used.
Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).
The proportion of component [C] used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of copolymer [A]. When the amount used exceeds 20 parts by weight, precipitates may be deposited in the coating film forming step, which may hinder the coating film formation.

Examples of the polymerizable compound [D] having at least one ethylenically unsaturated double bond (hereinafter sometimes referred to as “component D”) include monofunctional (meth) acrylate and bifunctional (meth) acrylate. Alternatively, trifunctional or higher functional (meth) acrylates can be preferably exemplified.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate. As these commercial products, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.) ) Co., Ltd.), Biscoat 158, 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate. As these commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku) Medicine Co., Ltd.), Viscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industries, Ltd.).

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Co., Ltd.), screw Over DOO 295, the 300, the 360, the GPT, said 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

Of these, a tri- or higher functional (meth) acrylate is preferably used, and among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.
These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination. The proportion of the component [D] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By including the component [D] at such a ratio, the heat resistance and surface hardness of the protrusions and / or spacers obtained from the radiation-sensitive resin composition of the present invention can be improved. If the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a coating film of the radiation-sensitive resin composition on the substrate.

The epoxy resin other than the above [E] copolymer [A] (hereinafter sometimes referred to as “E component”) is not limited as long as the compatibility is not affected, but is preferably a bisphenol A type. Epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, resins obtained by (co) polymerization of glycidyl methacrylate, etc. Can be mentioned. Of these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.
[E] The usage-amount of a component becomes like this. Preferably it is 30 weight part or less with respect to 100 weight part of copolymers [A]. By containing the component [E] at such a ratio, the heat resistance and surface hardness of the protrusions and / or spacers obtained from the radiation-sensitive resin composition of the present invention can be further improved. When this ratio exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when a coating film of the radiation sensitive resin composition is formed on the substrate.
The copolymer [A] can also be referred to as an “epoxy resin”, but differs from the component [E] in that it has alkali solubility.

In the radiation sensitive resin composition of the present invention, the above-mentioned [F] surfactant can be used in order to further improve the coating property. As the [F] surfactant that can be used here, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be suitably used.
Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8 , 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Sodium sulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates; fluorinated alkyl esters be able to. These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, D -57, DC-190 (manufactured by Toray Silicone Co., Ltd.), and the like.

  Examples of the silicone surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH30PA, FS-1265-300 (above, Toray Dow Corning Silicone Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, manufactured by GE Toshiba Silicone Co., Ltd.) and the like. Can do.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (Kyoeisha Chemical Co., Ltd.) ))) Can be used.
These surfactants can be used alone or in combination of two or more.
These [F] surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer [A]. [F] When the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.

  In the radiation sensitive resin composition of the present invention, [G] an adhesion assistant can also be used in order to improve the adhesion to the substrate. As such [G] adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such [G] adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where a development residue is likely to occur in the development process.

The [H] cross-linking agent forms a cross-linked structure between molecules of the specific alkali-soluble resin that is the [A] component. Examples of such crosslinking agents include condensation products of urea and formaldehyde (hereinafter also referred to as “urea-formaldehyde condensation products”), condensation products of melamine and formaldehyde (hereinafter referred to as “melamine-formaldehyde condensation products”). Also, methylol urea alkyl ethers and methylol melamine alkyl ethers obtained from these condensation products and alcohols can be used.
Specific examples of the urea-formaldehyde condensation product include monomethylol urea and dimethylol urea.
Specific examples of the melamine-formaldehyde condensation product include hexamethylol melamine. In addition to this, a product in which melamine and formaldehyde are partially condensed may be used.
The methylol urea alkyl ethers are obtained by reacting alcohols with some or all of the methylol groups in the urea-formaldehyde condensation product. Specific examples thereof include monomethylol urea methyl ether and dimethylol urea methyl. Examples include ether.
The methylol melamine alkyl ethers are obtained by reacting alcohols such as methyl alcohol and n-butyl alcohol with some or all of hydroxymethyl groups in the melamine-formaldehyde condensation product. Hexamethylol melamine hexamethyl ether, hexamethylol melamine hexa n-butyl ether, a compound having a structure in which the hydrogen atom of the amino group of melamine is substituted with a hydroxymethyl group and a methoxymethyl group, and the hydrogen atom of the amino group of melamine is butoxy Examples thereof include compounds having a structure substituted with a methyl group and a methoxymethyl group.
Among these, methylol melamine alkyl ethers are preferably used, and as commercially available products of such methylol melamine alkyl ethers, “Cymel 300”, “Cymel 370”, “Cymel 232” manufactured by Mitsui Cytec Co., Ltd. , “My Coat 505” and the like.
The proportion of component [H] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, relative to 100 parts by weight of component [A].
When this ratio exceeds 50 parts by weight, the thickness of the unirradiated portion of the coating film in the development process may be significantly reduced, and the transparency of the resulting coating film may be reduced.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned copolymer [A] and [B] components and other components optionally added as described above. Is done. Usually, the radiation sensitive resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition in a solution state can be prepared by mixing the copolymer [A] and [B] components and other optionally added components in a predetermined ratio.
As a solvent used for the preparation of the radiation sensitive resin composition of the present invention, each component of the copolymer [A] and [B] components and other components optionally blended is uniformly dissolved, and each component Those that do not react with.

As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.
Of these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferred from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. Used. Of these, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution (that is, the total of the copolymer [A] and [B] components and other components optionally added) The ratio of (amount) can be arbitrarily set depending on the purpose of use, the value of the desired film thickness, etc., but is usually 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight. %.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of protrusions and / or spacers Next, a method for forming the protrusions and / or spacers of the present invention using the radiation-sensitive resin composition of the present invention will be described. The method for forming protrusions and / or spacers of the present invention includes at least the following steps.
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of irradiating at least a part of the coating film with radiation.
(3) Development process.
(4) Heating process.

(1) Step of forming a coating film of the radiation-sensitive composition of the present invention on a substrate In the step of (1) above, the solvent is removed by applying the composition solution of the present invention to the substrate surface and performing pre-baking. The coating of the radiation sensitive resin composition is formed by removing.
Examples of the substrate that can be used in the present invention include a glass substrate, a silicon wafer, and a substrate on which various metals are formed.
The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. In particular, spin coating and slit die coating are preferred. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.

(2) Step of irradiating at least a part of the coating film In the step (2), the developer is irradiated with radiation through a mask having a predetermined pattern on the formed coating film. The patterning is performed by removing the irradiated portion using the development process. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation including g-line and / or i-line is particularly preferable.
As a pattern mask used for exposure and an exposure operation, (a) a method of performing exposure once using one type of photomask having both patterns of a protruding portion and a spacer portion (the smaller the portion to be masked, the more light leaks) (B) A difference in height is formed in combination with the melt flow during baking.) (B) A photomask having only a protruding portion and a photomask having only a spacer portion. Any of the methods of using and exposing twice may be used. In addition, as the pattern mask used in the method (A), it is possible to use a mask having different transmittances between the protruding portion and the spacer portion. However, in the present invention, depending on circumstances, only one of the protrusion and the spacer may be formed on the substrate. In this case, (c) a photomask having only the protrusion and a photomask having only the spacer. A method of performing exposure once using either one is employed. In this case, the remaining protrusions or spacers necessary for the vertical alignment type liquid crystal display element are formed by a conventionally known method.

(3) Development process Developers used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, An aqueous solution of an alkali such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution described above, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. . Furthermore, as a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time is usually 30 to 180 seconds, although it varies depending on the composition of the composition.

(4) Heating step (3) Performed as described above (3) After the development step, the patterned thin film is preferably rinsed, for example, by washing with running water, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediadito compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) with a heating device such as a hot plate or an oven. Then, the thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more can be used.
In this way, a patterned thin film corresponding to the target protrusion and / or spacer can be formed on the surface of the substrate.

  The height of the protrusions thus formed is usually 0.1 to 3.0 μm, preferably 0.5 to 2.0 μm, particularly preferably 1.0 to 1.5 μm, and the height of the spacer The thickness is usually 1 to 10 μm, preferably 2 to 8 μm, particularly preferably 3 to 5 μm.

  According to the method for forming protrusions and / or spacers for the vertical alignment type liquid crystal display element of the present invention, fine processing is possible, and the shape and size (height and bottom dimensions) can be easily controlled, and the pattern shape A vertical alignment type liquid crystal display element capable of stably forming fine protrusions and spacers excellent in heat resistance, solvent resistance, transparency, etc. with good productivity and excellent in orientation, voltage holding ratio, etc. Can bring.

  The radiation-sensitive resin composition for forming protrusions and / or spacers for the vertical alignment type liquid crystal display element of the present invention has excellent resolution and residual film ratio, and has a pattern shape, heat resistance, solvent resistance, and transparency. Thus, it is possible to form a vertical alignment type liquid crystal display element having excellent alignment and voltage holding ratio. In addition, the method for forming the protrusions and / or spacers for the vertical alignment type liquid crystal display element of the present invention can be finely processed, and the shape and size (height, bottom dimension, etc.) can be easily controlled. Fine projections and spacers excellent in heat resistance, solvent resistance, transparency, etc. can be stably formed with good productivity, and a vertical alignment type liquid crystal display element excellent in orientation, voltage holding ratio, etc. is provided. be able to.

The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
Synthesis example of copolymer [A] Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by weight of styrene, 14 parts by weight of methacrylic acid, 11 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 25 parts by weight of tetrahydrofurfuryl methacrylate, 45 parts by weight of glycidyl methacrylate, And after 5 parts by weight of α-methylstyrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1].
The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-1] was 8,000. The solid content concentration of the polymer solution obtained here was 29.8% by weight.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 18 parts by weight of methacrylic acid, 6 parts by weight of styrene, 11 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 30 parts by weight of glycidyl methacrylate, 15 parts by weight of p-vinylbenzylglycidyl ether. Parts, 20 parts by weight of tetrahydrofurfuryl methacrylate, and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2].
The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-2] was 11,000. The solid content concentration of the polymer solution obtained here was 31.5% by weight.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 18 parts by weight of glycidyl methacrylate, ⁶ parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 30 parts by weight of p-vinylbenzylglycidyl ether, polyethylene glycol ( n = 2) After 30 parts by weight of monomethacrylate and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing the copolymer [A-3].
The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-3] was 13,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.7% by weight.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 8.5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, 15 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of polyethylene glycol (n = 3) monomethacrylate and After 3 parts by weight of α-methylstyrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing the copolymer [A-4].
The copolymer [A-4] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000. Further, the solid content concentration of the polymer solution obtained here was 31.5% by weight.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 15 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2-methyl-tetrahydro-2-oxo 2-propenoate After adding 20 parts by weight of -3-furanyl ester and 3 parts by weight of α-methylstyrene dimer and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-5].
The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-5] was 9,000. The polymer solution obtained here had a solid content concentration of 31.7% by weight.

Example 1
[Preparation of radiation-sensitive resin composition]
The solution containing the polymer [A-1] as the [A] component synthesized in Synthesis Example 1 above, as the amount corresponding to 100 parts by weight (solid content) of the polymer [A-1], and the component [B] 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) of a condensate (B-1) (30 parts by weight) was mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by weight, and then a membrane filter having a diameter of 0.2 μm. The solution (S-1) of the radiation sensitive resin composition was prepared by filtration.

Examples 2-10
In Example 1, a solution of the radiation-sensitive resin composition was carried out in the same manner as in Example 1 except that the types and amounts shown in Table 1 were used as the [A] component and the [B] component. (S-2) to (S-10) were prepared.
In Table 1, the abbreviations of the components indicate the following compounds.
(B-1): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensate (B-2) of -5-sulfonic acid chloride (2.0 mol): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene Condensation product of bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) (B-3): 2,3,4,4′-tetrahydroxybenzophenone (1 .0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol)
(B-4): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide -4-Sulphonic acid chloride (2.0 mol) condensate (F): SH28PA (manufactured by Dow Corning Toray Silicone Co., Ltd.)

Using the radiation-sensitive resin composition prepared as described above, protrusions and spacers were formed as follows, and various characteristics were evaluated.
[Formation of protrusions and spacers]
After applying the composition on the silicon substrate using Examples 11-19 using a spinner and Examples 20-24 using a slit die coater, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 4 A coating film of 0.0 μm was formed. After that, exposure is performed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a photomask having a remaining pattern of 5 μm width corresponding to the protruding portion and a remaining pattern of 30 μm dots corresponding to the spacer portion. Exposure was carried out by changing the time. Thereafter, development was carried out for 100 seconds using the developer type, developer concentration, and development method described in the table, followed by washing with pure water for 1 minute and drying to form a pattern on the wafer. At this time, the exposure amount required to form a 5 μm-width remaining pattern corresponding to the protruding portion and a 30 μm-dot remaining pattern corresponding to the spacer portion was measured. This value is shown in the table as sensitivity. It can be said that the sensitivity is good when this value is 3500 J / m ² or less.

(Evaluation of cross-sectional shape of protrusions)
When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed with a scanning electron microscope, and the case of A or B is “good” and the case of C is “ “Bad”. The cross-sectional shapes A, B and C of the protrusions are typically as illustrated in FIG.
A: When the dimension of the bottom is more than 5 μm and 7 μm or less,
B: When the bottom dimension exceeds 7 μm,
C: A trapezoidal shape regardless of the size of the bottom.

[Evaluation of spacer cross-section]
When the cross-sectional shapes A, B and C of the spacer are defined as follows, the cross-sectional shape of the formed spacer is observed with a scanning electron microscope, and the case of A or C is “good” and the case of B is “ “Bad”. The cross-sectional shapes A, B and C of the spacer are schematically as illustrated in FIG.
A: When the dimension of the bottom is more than 30 μm and not more than 36 μm,
B: When the bottom dimension exceeds 36 μm,
C: A trapezoidal shape regardless of the size of the bottom.

[Evaluation of solvent resistance]
After applying the composition on a silicon substrate using Examples 11-19 using a spinner and Examples 20-24 using a slit die coater, the film was prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 3 A coating film of 0.0 μm was formed. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and this silicon substrate was exposed to 220 in a clean oven. A cured film was obtained by heating at 0 ° C. for 1 hour. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion { | T1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the solvent resistance is good.
In the evaluation of solvent resistance, since the patterning of the film to be formed is unnecessary, the radiation irradiation process and the development process were omitted, and only the coating film forming process, the post-baking process, and the heating process were performed for evaluation.

[Evaluation of heat resistance]
A cured film was formed in the same manner as the evaluation of the solvent resistance, and the film thickness (T2) of the obtained cured film was measured. Next, this cured film substrate was additionally baked in a clean oven at 240 ° C. for 1 hour, and then the film thickness (t2) of the cured film was measured, and the film thickness change rate {| t2-T2 | / T2 due to the additional baking. } × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the heat resistance is good.

[Evaluation of transparency]
In the evaluation of the solvent resistance, a cured film was formed on the glass substrate in the same manner except that a glass substrate “Corning 7059 (manufactured by Corning)” was used instead of the silicon substrate. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Table 2 shows the values of the minimum light transmittance at that time. When this value is 90% or more, it can be said that the transparency is good.

[Evaluation of orientation and voltage holding ratio]
Using the composition solution, protrusions and spacers were formed on the electrode surface of a glass substrate having an ITO (tin-doped indium oxide) film as an electrode in the same manner as described above. Thereafter, AL1H659 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal alignment agent was applied to a glass substrate on which protrusions and spacers were formed with a liquid crystal alignment film coating printer, and then dried at 180 ° C. for 1 hour. A film having a thickness of 0.05 μm was formed. Moreover, AL1H659 as a liquid crystal aligning agent is apply | coated to the electrode surface of another glass substrate which has an ITO film | membrane with a printer for liquid crystal aligning film application | coating, and it dries at 180 degreeC for 1 hour, and forms a 0.05-micrometer-thick film. Formed.
Next, an epoxy resin adhesive with a glass fiber having a diameter of 5 μm is applied to the outer surfaces of the liquid crystal alignment films of both substrates obtained by screen printing, and the substrates are stacked and bonded so that the liquid crystal alignment film surfaces face each other. After that, the adhesive was cured. Then, after filling the liquid crystal MLC-6608 (trade name) manufactured by Merck Co., Ltd. between both substrates from the liquid crystal injection port, and sealing the liquid crystal injection port with an epoxy-based adhesive, a polarizing plate is placed on the outer surfaces of both substrates. The vertically aligned liquid crystal display elements were manufactured by pasting them so that their deflection directions were orthogonal. FIG. 2 schematically shows a longitudinal sectional view of the obtained vertical alignment type liquid crystal display element.
Next, the orientation and voltage holding ratio of the obtained vertical alignment type liquid crystal display element were evaluated as follows.

In the evaluation of the orientation, when a voltage was turned on / off, whether or not an abnormal domain was generated in the liquid crystal cell was observed with a polarizing microscope. In evaluating the voltage holding ratio, a voltage of 5 V was applied to the liquid crystal display element, the circuit was opened, the holding voltage after 16.7 milliseconds was measured, and the ratio to the applied voltage (5 V). Was calculated. When the value is 98% or more, it can be said that it is good.

It is a schematic diagram which illustrates the cross-sectional shape of protrusion and a spacer.

It is a schematic diagram which illustrates the cross-sectional shape of the vertical alignment type liquid crystal display element which has a processus | protrusion and a spacer. 1 spacer, 2 protrusions, 3 liquid crystal, 4 liquid crystal alignment film, 5 color filter, 6 glass substrate

Claims (5)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, lactone skeleton, Unsaturated compounds (a4) (a1), (a2) and (a3) containing at least one group selected from the group consisting of an oxyethylene skeleton having 2 to 10 repeating units and an oxypropylene skeleton having 2 to 10 repeating units And a copolymer of an olefinically unsaturated compound other than (B), and [B] 1,2-quinonediazide compound, and a sensation for forming protrusions and / or spacers for a vertical alignment type liquid crystal display device Radiation resin composition. A protrusion for a vertical alignment type liquid crystal display element formed from the radiation-sensitive resin composition according to claim 1. A spacer for a vertical alignment type liquid crystal display element formed from the radiation-sensitive resin composition according to claim 1. A vertical alignment type liquid crystal display device comprising the protrusion according to claim 2 and / or the spacer according to claim 3. A method for forming protrusions and / or spacers, comprising at least the following steps.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate.
(2) A step of irradiating at least a part of the coating film with radiation.
(3) Development process.
(4) Heating process.

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